Metal complexes of isoindolinazines, process for their preparation and use

ABSTRACT

1:1 metal complexes of azines of the formula ##STR1## in which the ring A can be further substituted, R is an H atom or an alkyl or aryl group, B is an isocyclic or heterocyclic aromatic radical or an alicyclic radical, R 1  is the OH or SH group and Y is a radical of the formula ##STR2## in which Z is an O or S atom, n is the number 1 or 2 and R 2  is an alkyl, aralkyl, cycloalkyl or aryl radical or an amino group which is unsubstituted or substituted by an alkyl, cycloalkyl, aralkyl or aryl radical. 
     In plastics and surface coatings, the novel pigments give intense pure orange to violet colorations with good fastness properties.

The invention relates to 1:1 metal complexes of isoindolinazines of the formula ##STR3## in which the ring A can be further substituted, R is an H atom or an alkyl or aryl group, B is an isocyclic or heterocyclic aromatic radical or an alicyclic radical, R₁ is the OH or SH group and Y is a radical of the formula ##STR4## in which Z is an O or S atom, n is the number 1 or 2 and R₂ is an alkyl, aralkyl, cycloalkyl or aryl radical or an amino group which is unsubstituted or substituted by an alkyl, cycloalkyl, aralkyl or aryl radical.

As substituents in the benzene ring A, the isoindolinonazines (sic) of the formula (1) can contain halogen atoms, for example 2-4 chlorine atoms, 1-2 alkyl or alkoxy groups having 1-4 C, a phenyl, phenoxy, nitro or benzoylamino group or an alkanoylamino group having 2-6 C, but they are preferably unsubstituted.

R is, for example, a phenyl or naphthyl radical and preferably an H atom or an alkyl group having 1-4 C, in particular the methyl group.

B is, for example, a phenylene or naphthylene radical, but especially a 5-6-membered heterocyclic ring, which may or may not be fused, containing an N, O, or S atom in the β-position to the C* atom, and, if desired, a further N atom in the ring. B is, for example, a pyrazole, pyrimidine, quinoline or coumarin ring. R₁ is preferably the hydroxyl group. An alicyclic radical B is preferably a cyclohexyl radical.

An alkyl radical R₂ preferably has 1-4 C. A cycloalkyl radical R₂ is in particular the cyclohexyl radical. An aryl radical R₂ is, for example, a naphthyl and especially phenyl radical. An amino group R₂ is preferably substituted by an alkyl group having 1-4 C, a cyclohexyl group or a phenyl or benzyl group.

Preferred metal complexes are those of the formula ##STR5## in which M is nickel or copper, R' is H or methyl, B' is a pyrazole, pyrimidine, quinoline or coumarin radical and Y' is a radical of the formula ##STR6## in which R₃ is an H atom, an alkyl group having 1-4 C or a radical of the formula ##STR7## in which X₁ is an H, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulfamoyl group, an alkyl, alkoxy or alkylsulfamoyl group having 1-4 C, an alkanoylamino, alkylcarbamoyl or alkoxycarbonyl group having 2-6 C, or a phenoxy, phenylcarbamoyl or phenylsulfamoyl group which is unsubstituted or substituted by chlorine or bromine atoms or methyl groups, and X₂ is an H, chlorine or bromine atom or an alkyl or alkoxy group having 1-4 C.

Metal complexes which are also preferred are those of the formula (3) in which Y' is a radical of the formula ##STR8## in which Z is O or S and R₄ is an alkyl group having 1-4 C, a cyclohexyl or benzyl group or a group of the formula (5).

The formulae (1) and (3) represent only one of the various isomeric forms.

The metal complexes of the formula (1) are obtained by (a) treating an azine of the formula (1) with metal donors or (b) heating a hydrazone of the formula ##STR9## in which R, R₁ and B are as defined, with an isoindolinone of the formula ##STR10## or an amino-isoindolenine of the formula ##STR11## in which R₅ and R₆ are H atoms or alkyl, aryl or heteroaryl groups, or R₅ and R₆, together with the N atom, are a heterocyclic 5- or 6-membered ring, and A and Y are as defined, in the presence of metal donors, in a polar organic solvent.

Alkyl radicals R₅ and R₆ preferably have 1-6 C. An aryl radical R₆ is preferably a phenyl radical which is unsubstituted or substituted by chlorine atoms or alkyl or alkoxy groups having 1-4 C.

The azines of the formula (1) are obtained, for example, by the process described in British Pat. No. 1,467,595, wherein a hydrazone of the formula (6) is condensed with an amino-isoindolenine of the formula (8) in which A and Y are as defined and R₅ ═R₆ ═H.

The compound of the formula (8) is obtained by condensing the methine-imino-isoindolenine of the formula ##STR12## with an amine of the formula ##STR13## in which A, Y, R₅ and R₆ are as defined. The compound of the formula (9) is in turn obtained by reacting the amino-imino-isoindoline of the formula ##STR14## with a compound of the formula ##STR15## in which A, Z, n and R₂ are as defined. Examples of amino-imino-isoindolinone (sic) are those listed on page 5 of British Pat. No. 1,465,595.

Examples of compounds of the formula (11) are: NCCH₂ CSCH₃, NCCH₂ CSC₂ H₅, NCCH₂ CSCH₂ CH₂ CH₃, NCCH₂ CSCH(CH₃)₃, NCCH₂ CS(CH₂)₃ CH₃, NCCH₂ CSCH₂ CH(CH₃)₂, NCCH₂ CSCH₂ C₆ H₅, NCCH₂ CS-cyclohexyl, NCCH₂ --CS-phenyl, NCCH₂ CS--(o-, m- or p)-chlorophenyl, NCCH₂ CSNH₂, NCCH₂ CSNHCH₃, NCCH₂ CSNHC₂ H₅, NCCH₂ CSNHCH(CH₃)₂, NCCH₂ CSNH(CH₂)₃ CH₃, NCCH₂ CSNHCH₂ (CH₃)₂, NCCH₂ --CSNH-cyclohexyl, NCCH₂ CSNHCH₂ C₆ H₅, NCCH₂ --CSNH-phenyl, NCCH₂ --CSNH--(o-, m- or p)-chlorophenyl, NCCH₂ CSNH--(o-, m- or p)-methylphenyl, NCCH₂ CSNH--(o-, m- or p)-methoxyphenyl, NCCH₂ CSNH--α-naphthyl, NCCH₂ CSNHCOCH₃, NCCH₂ CSNHCO-phenyl, NCCH₂ CSNHCONHC₂ H₅, NCCH₂ CSNHCONHC₆ H₅ and NCCH₂ CSNHCSNHC₆ H₅.

The N-substituted thiocarbamoylacetonitrile derivatives can be prepared, inter alia, by the known process (A. D. Grabenko et at., Zh. Obshch. Khim. 32 (1962) 2,248, c.f. Chem. Abstr. 58, 5546g, 7863e) of reacting cyanoacetic acid esters with the corresponding isothiocyanate, followed by hydrolysis and decarboxylation.

The hydrazones of the formula (6) are obtained by the known process of reacting the oxo compound of the formula ##STR16## in which R, R₁ and B are as defined, or its imines or preferably anils, with hydrazine hydrate.

Examples of oxo compounds of the formula (11) are the aldehydes and ketones listed on pages 11 and 12 of British Pat. No. 1,467,595 and also 2-formyl-5,5-dimethylcyclohexane-1,3-dione and 1-phenyl-3-methyl-4-formyl-5-mercapto-pyrazole.

The isoindolinones of the formula (7) used as starting materials for method (b) are obtained by reacting the imino-isoindolinones of the formula ##STR17## in which A is as defined, a phthalodinitrile or an o-cyanobenzoic acid ester with compounds of the formula (10) by known processes.

The metal donors used are preferably salts of zinc, cadmium, manganese, cobalt and iron, but especially of copper and nickel, or of mixtures of these metals. The formates, acetates or stearates of these metals are advantageously used.

The reactions take place in a polar solvent, in particular one of a hydrophilic nature, for example an amide, such as dimethylformamide, formamide, dimethylacetamide or N-methylpyrrolidone, or also dimethyl sulfoxide, acetonitrile or an alcohol, for example ethylcellosolve. It is also possible to use a mixture of polar solvents.

The reaction temperature is advantageously between 100° to 200° C.

The metal complex obtained is isolated in the customary manner by filtration. The material on the suction filter is washed thoroughly with solvent. It is obtained in excellent yield and purity and can be used without further purification, in finely divided form, for colouring high-molecular organic material, for example cellulose ethers and esters, such as ethylcellulose, acetylcellulose and nitrocellulose, polyamides, polyurethanes or polyesters, and natural resins or synthetic resins, for example aminoplasts, in particular urea/formaldehyde and melamine/formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile and polyacrylic acid esters, thermoplastic or curable acrylic resins, rubber, casein, silicone and silicone warts (sic), individually or in mixtures. The high-molecular compounds mentioned can be in the form of plastic masses or melts or in the form of spinning solutions, surface coatings or printing inks. Depending on the intended use, it proves advantageous to use the novel pigments as toners or in the form of preparations.

The pigment can be employed in the form in which it is obtained in the synthesis, or in a lightly ground form, in which case it produces opaque final colorations. However, it can also be subjected to intensive grinding, in which case transparent final colorations, for example intensely coloured metallic-effect coatings, are obtained.

Pastes of the pigments in surface coatings are distinguished by favourable flow properties.

The colorations obtained, for example in plastics, fibres and surface coatings, are distinguished by high colour intensity, high purity of colour shade, good dispersibility and good fastness to overcoating, migration, heat, light and weather, and also by a good gloss.

In the following examples, percentages are by weight and degrees are degrees centigrade.

Example 1

12.21 g (0.04 mol) of 1-(cyano-phenylthiocarbamoylmethylene)-3-oxo-isoindoline, prepared from 1-imino-3-oxo-isoindoline and cyanothioacetanilide, 10.03 g (0.04 mol) of 1-p-chlorophenyl-3-methyl-4-hydrazinomethylene-5-pyrazolone and 10.5 g (0.042 mol) of nickel acetate.4H₂ O are successively suspended in 400 ml of dimethylformamide. The resulting suspension is heated to 120° C. and stirred at the same temperature for 2 hours. The mixture is then cooled to 80° C. and the metal complex obtained as a thick precipitate is filtered off. The material on the suction filter is washed with dimethylformamide and ethanol and dried in vacuo at 80° C. In this way, 22.2 g (93.3% of theory) of the 1:1 nickel complex of the formula ##STR18## are obtained.

    ______________________________________                                         Microanalysis: C.sub.28 H.sub.18 ClN.sub.7 OSNi MW 594.72                      calculated*                                                                            C 54.8%  H 3.3%   N 16.0%                                                                               S 5.23%                                                                               Ni 9.58%                               found   C 54.7%  H 3.1%   N 16.5%                                                                               S 5.5% Ni 9.43%                               ______________________________________                                          *taking into account the amount of H.sub.2 O found, i.e. 2.9%            

The above metal complex pigment colours plastics and surface coatings in red shades with excellent fastness properties.

Example 2

1.95 g (0.008 mol) of 2-anilinomethylene-5,5-dimethylcyclohexane-1,3-dione are dissolved in 50 ml of dimethylformamide and treated with 0.4 ml of hydrazine hydrate and the mixture is then stirred for 1 hour at room temperature. 2.1 g (0.0084 mol) of nickel acetate.4H₂ O are added and the mixture is warmed to 60° C. The resulting suspension is treated with 2.44 g (0.008 mol) of 1-(cyano-N-phenylthiocarbamoylmethylene)-3-isoindolinone, warmed to 120° C. and stirred at the same temperature for 1 hours. After cooling the reaction mixture to 80° C., the metal complex which has precipitated out is filtered off, washed with dimethylformamide and ethanol and finally dried overnight at 80° C. in vacuo. 3.5 g (83% of theory) of a red pigment of the composition ##STR19## are obtained.

    ______________________________________                                         Microanalysis: C.sub.26 H.sub.21 N.sub.5 O.sub.2 SNi MW                        ______________________________________                                         526                                                                            calcu-                                                                         ated: 59.34% C 4.02% H  13.31% N                                                                               6.09% S                                                                               11.16% Ni                               found:                                                                               59.2%  C 4.2%  H  13.5%  N                                                                               6.5%  S                                                                               11.3%  Ni                               ______________________________________                                    

The above metal complex colours plastics and surface coatings in orange shades with excellent fastness properties.

Example 3

If the procedure of Example 2 is repeated, except that 1-(cyano-thiocarbamoylmethylene)-3-isoindolinone is used in place of the 1-(cyano-N-phenylthiocarbamoylmethylene)-3-isoindolinone, 2.3 g (64% of theory) of an orange-red complex of the composition ##STR20## are obtained.

    ______________________________________                                         Microanalysis: C.sub.20 H.sub.17 N.sub.5 O.sub.2 SNi MW                        ______________________________________                                         450                                                                            calcu-                                                                         lated:                                                                               53.36% C 3.81% H  15.56% N                                                                               7.12% S                                                                               13.04% Ni                               found:                                                                               53.5%  C 3.8%  H  15.8%  N                                                                               7.1%  S                                                                               13.0%  Ni                               ______________________________________                                    

The above pigment colours plastics and surface coatings in orange shades with a high level of fastness.

Example 4

1.72 g (0.007 mol) of 1-phenyl-3-carbamoyl-4-hydrazinomethylene-pyrazol-5-one are suspended with 1.83 g (0.00735 mol) of nickel acetate.4H₂ O in 30 ml of N-methylpyrrolidone and the suspension is then warmed to 60° C. 2.14 g (0.007 mol) of 1-(cyano-N-phenylthiocarbamoylmethylene)-3-isoindolinone are added and the mixture is heated to 115° C. and left to react at the same temperature for 2 hours. It is then cooled to 80° C. and the product which has precipitated out is filtered off. After washing with N-methylpyrrolidone and ethanol and drying at 80° C. in vacuo, 2.6 g (67% of theory) of a wine-red metal complex of the structure ##STR21## are obtained.

    ______________________________________                                         Microanalysis: C.sub.28 H.sub.18 N.sub.8 O.sub.2 SNi MW                        ______________________________________                                         589                                                                            calcu-                                                                         lated:                                                                               57.07% C 3.08% H  19.01% N                                                                               5.44% S                                                                               9.96% Ni                                found:                                                                               57.2%  C 3.2%  H  19.2%  N                                                                               5.3%  S                                                                               9.8%  Ni                                ______________________________________                                    

When incorporated into plastics and surface coatings, the above pigment produces red shades with excellent fastness properties.

Example 5

1.3 g (0.006 mol) of 2,4-dihydroxy-3-acetylquinoline-hydrazone and 1.57 g (0.0063 mol) of nickel acetate. 4H₂ O are suspended in 50 ml of dimethylformamide. After warming to 60° C., 1.82 g (0.006 mol) of 1-(cyanothiocarbamoylmethylene)-5,6-dichloro-3-isoindolinone are added, with stirring, and the mixture is heated further to 105° C. and left to react for 2 hours at the same temperature. It is then cooled to 80° C. and the metal complex which has precipitated out is filtered off, washed with dimethylformamide and ethanol and dried overnight at 80° C. in vacuo. 3.2 g (96% of theory) of a red metal complex of the composition C₂₂ H₁₂ Cl₂ N₆ O₂ SNi and the structure ##STR22## are obtained.

    __________________________________________________________________________     Microanalysis: C.sub.22 H.sub.12 Cl.sub.2 N.sub.6 O.sub.2 SNi MW               __________________________________________________________________________     554                                                                            calcu-                                                                         lated:                                                                              47.69% C                                                                            2.18% H                                                                             15.17% N                                                                            5.79% S                                                                             12.80% Cl                                                                            10.60% Ni                                       found:                                                                              47.2%  C                                                                            2.4% 15.3%  N                                                                            5.5% 12.4% Cl                                                                             10.3% Ni                                        __________________________________________________________________________

The above pigment colours plastics and surface coatings in bluish red shades with excellent fastness properties.

Example 6

0.4 ml of hydrazine hydrate (0.008 mol) is added to a solution of 2.35 g (0.008 mol) of 1-phenyl-3-methyl-4-anilinomethylene-5-thiopyrazolone in 50 ml of dimethylformamide and the mixture is stirred at room temperature for 1 hour. After the further addition of 2.1 g (0.0084 mol) of nickel acetate.4H₂ O, the reaction (sic) mixture is warmed to 60° C. and then treated with 2.44 g (0.008 mol) of 1-(cyano-N-phenylthiocarbamoylmethylene)-3-isoindolinone. The mixture is left to react at 120° C. for 1 hour and then cooled to 80° C. and filtered. The filtration residue is washed with dimethylformamide and ethanol and dried overnight at 80° C. in vacuo. 2.2 g (48% of theory) of a reddish brown metal complex of the composition ##STR23## are obtained.

    ______________________________________                                         Microanalysis: C.sub.28 H.sub.19 N.sub.7 S.sub.2 Ni MW 576                     ______________________________________                                         calcu-                                                                         lated: 58.35% C 3.32% H  17.01% N                                                                              11.13% S                                                                              10.19% Ni                               found: 57.8%  C 3.4%  H  17.1%  N                                                                              11.1%  S                                                                              10.3% Ni                                ______________________________________                                    

Examples 7-35

Analogously to Examples 1-6, further 1:1 nickel complexes are obtained by condensing the hydrazone of the oxo compounds indicated in column 2 of the table with the isoindolinone of the formula ##STR24## the latter having been obtained by condensing the 3-imino-isoindolinone mentioned in column 3 with the compounds YH₂ listed in column 4. Column 5 gives the shade in PVC.

                                      TABLE 1                                      __________________________________________________________________________     Ex-                                                                            ample                                      Shade in                            No. Oxo compound                                                                               Isoindolinone                                                                              YH.sub.2       PVC                                 __________________________________________________________________________     7   3-Acetyl-2,4-dihydroxy-                                                                    3-Imino-isoindolinone                                                                      Cyanomethylthiocarb-p-                                                                        red                                     quinoline               chloroanilide                                      8   3-Acetyl-2,4-dihydroxy-                                                                    3-Imino-isoindolinone                                                                      Cyanomethylthiocarb-p-                                                                        red                                     quinoline               toluidide                                          9   3-Acetyl-2,4-dihydroxy-                                                                    3-Imino-isoindolinone                                                                      Cyanomethylthiocarb-p-                                                                        red                                     quinoline               anisidide                                          10  1-p-Chlorophenyl-3-                                                                        3-Imino-isoindoline                                                                        Cyanomethylthiocarbanilide                                                                    red                                     methyl-4-formyl-                                                               pyrazal-5-one (sic)                                                        11  3-Acetyl-2,4-dihydroxy-                                                                    3-Imino-isoindoline                                                                        Cyanomethylthiocarbanilide                                                                    red                                     quinoline                                                                  12  3-Acetyl-2,4-dihydroxy-                                                                    3-Imino-isoindoline                                                                        Cyanomethylthiocarbanilide                                                                    red                                     quinoline                                                                  13  5-Acetyl-2,4,6-di-                                                                         3-Imino-isoindoline                                                                        Cyanomethylthiocarbanilide                                                                    orange                                  hydroxy-pyrimidine                                                         14  3-Acetyl-4-hydroxy-                                                                        3-Imino-isoindoline                                                                        Cyanomethylthiocarbanilide                                                                    red                                     coumarin                                                                   15  1-(2',4',6' -trichloro-                                                                    3-Imino-isoindolinone                                                                      Cyanomethylthiocarbanilide                                                                    red                                     phenyl)-3-methyl-4-                                                            formyl-pyrazol-5-one                                                       16  1-(3',4'-dichloro-                                                                         3-Imino-isoindolinone                                                                      Cyanomethylthiocarbanilide                                                                    red                                     phenyl)-3-methyl-4-                                                            acetyl-pyrazol-5-one                                                       17  3-Acetyl-2,4-dihydroxy                                                                     3-Imino-isoindolinone                                                                      Cyanomethylthiocarbanilide                                                                    red                                     quinoline                                                                  18  5-Acetyl-2,4,6-tri-                                                                        3-Imino-isoindolinone                                                                      Cyanomethylthiocarbanilide                                                                    orange                                  hydroxy-pyrimidine                                                         19  3-Acetyl-4-hydroxy-                                                                        3-Imino-isoindolinone                                                                      Cyanomethylthiocarbanilide                                                                    red                                     coumanin                                                                   20  1-Phenyl-5-acetyl-4,6-                                                                     3-Imino-isoindolinone                                                                      Cyanomethylthiocarbanilide                                                                    red                                     dihydroxy-pyrimidine                                                       21  3-Acetyl-2,4-dihydroxy-                                                                    3-Imino-isoindolinone                                                                      Cyanomethylthiocarb-                                                                          red                                     quinoline               butylamide                                         22  3-Acetyl-4-hydroxy                                                                         3-Imino-isoindolinone                                                                      Cyanomethylthiocarb-                                                                          orange                                  coumarin                butylamide                                         23  3-Acetyl-4-hydroxy                                                                         3-Imino-isoindolinone                                                                      Cyanomethylthiocarb-                                                                          scarlet                                 coumarin                butylamide                                         24  1-p-Chlorophenyl-3-                                                                        3-Imino-isoindolinone                                                                      Cyanomethylthiocarb-                                                                          orange                                  methyl-4-acetyl-pyrazol-                                                                               butylamide                                             5-one                                                                      25  1-Methyl-3-acetyl-4-                                                                       3-Imino-isoindolinone                                                                      Cyanomethylthiocarb-                                   hydroxy-quinol-2-one    butylamide                                         26  3-Acetyl-2,4-dihydroxy-                                                                    3-Imino-4,5,6,7-tetra-                                                                     Cyanomethylthiocarb-                                                                          violet                                  quinoline   chloro-isoindolinone                                                                       butylamide                                         27  3-Acetyl-2,4-dihydroxy-                                                                    3-Imino-5,6-dichloro-                                                                      Cyanomethylthiocarb-                                                                          Bordeaux                                quinoline   isoindolinone                                                                              butylamide     red                                 28  1-p-Toyl-3-carbamoyl-                                                                      3-Imino-isoindolinone                                                                      Cyanomethylthiocarbamide                                                                      orange                                  4-formyl-pyrazol-5-one                                                     29  1-p-Toyl-3-carbamooyl-                                                                     3-Imino-isoindolinone                                                                      Cyanomethylthiocarbanilide                                                                    red                                     4-formyl-pyrazol-5-one                                                     30  1-Phenyl-3-acetylamino-                                                                    3-Imino-isoindolinone                                                                      Cyanomethylthiocarbanilide                                                                    brown                                   4-formyl-pyrazol-5-one                                                     31  1-p-Chlorophenyl-3-                                                                        3-Imino-isoindolinone                                                                      Cyanomethylthiocarbamide                                                                      orange                                  carbamoyl-4-formyl-                                                            pyrazol-5-one                                                              32  1-p-Chlorophenyl-3-                                                                        4,6-Dimethoxy-5,7-                                                                         Cyanomethylthiocarbamide                                                                      red                                     methyl-4-formyl-                                                                           dichloro-3-imino-iso-                                              pyrazol-5-one                                                                              indolinone                                                     33  1-p-Chlorophenyl-3-                                                                        5,6-Dichloro-3-imino-                                                                      Cyanomethylthiocarbamide                                                                      red                                     methyl-4-formyl-                                                                           isoindolinone                                                      pyrazol-s-one                                                              34  3-Acetyl-2,4-dihydroxy-                                                                    4,6-Dimethoxy-5,7-                                                                         Cyanomethylthiocarbamide                                                                      Bordeaux                                quinoline   dichloro-3-imino-          red                                                 isoindolinone                                                  35  3-Acetyl-4-hydroxy-                                                                        4,6-Dimethoxy-5,7-                                                                         Cyanomethylthiocarbamide                                                                      red                                     coumarin    dichloro-3-imino-                                                              isoindolinone                                                  __________________________________________________________________________

Example 36

25 parts of the pigment prepared according to Example 1, 100 parts of finely ground sodium chloride and 30 parts of diacetone-alcohol are initially introduced into a laboratory kneader with a capacity of 250 parts by volume. The mixture is kneaded for 5 hours, with cooling, and then introduced into 4,000 parts by volume of water. The sodium chloride and diacetone-alcohol dissolve and the pigment precipitates out. The suspension is filtered and the material on the suction filter is washed thoroughly with water and dried in a vacuum drying cabinet at 80°.

Example 37

1.09 g (0.005 mol) of 3-acetyl-2,4-dihydroxyquinoline-hydrazone and 1.31 g (0.00525 mol) of nickel acetate.4H₂ O are suspended in 100 ml of dimethylformamide. After warming to 60° C., 1.78 g (0.005 mol) of 1-(cyano-α-naphthyl-thiocarbamoyl-methylene)-3-oxo-isoindoline, prepared from cyanothioacetic acid α-naphthylamide and 1-imino-3-oxo-isoindoline, are added, with stirring. The reaction mixture is heated to 120° C., with stirring, and stirred at the same temperature for 2 hours. It is then cooled to 100° C. and the metal complex which has precipitated out is filtered off, washed with dimethylformamide and ethanol and dried overnight at 80° C. in vacuo. 2.9 g (97% of theory) of a red metal complex of the formula ##STR25## are obtained.

    ______________________________________                                         Microanalysis: C.sub.31 H.sub.20 N.sub.6 O.sub.2 SNi MW                        ______________________________________                                         599                                                                            calculated:                                                                             62.1% C  3.4% H   14.0% N                                                                               5.4% S                                                                               9.8 Ni                                 found:   62.7% C  3.7% H   13.9% N                                                                               5.7% S                                                                               9.6% Ni                                ______________________________________                                    

The above metal complex colours plastics and surface coatings in red shades with excellent fastness properties.

Example (sic) 38-47

Analogously to Example 41, further 1:1 nickel complexes listed in Table 2, of the formula ##STR26## in which R' and R'₃ are as defined in column 2 or 3, are obtained by reacting an isoindolinone of the formula ##STR27## with a hydrazone of the formula ##STR28## in the presence of nickel acetate.4H₂ O.

    ______________________________________                                         Ex-                                                                            am-                                  Shade                                     ple                                  in                                        No.   R'        R'.sub.3             PVC                                       ______________________________________                                         38                                                                                    ##STR29##                                                                               H                    red                                       39    "                                                                                         ##STR30##           bluish red                                40    CH.sub.3                                                                                  ##STR31##           bluish red                                41    "                                                                                         ##STR32##           bluish red                                42    "                                                                                         ##STR33##           bluish red                                43    CH.sub.3                                                                                  ##STR34##           bluish red                                44    "                                                                                         ##STR35##           bluish red                                45    "                                                                                         ##STR36##           bluish red                                46    "                                                                                         ##STR37##           bluish red                                47    "                                                                                         ##STR38##           red                                       ______________________________________                                    

Example 48

21.74 g (0.1 mol) of 3-acetyl-2,4-dihydroxyquinoline-hydrazone and 26.11 g (0.105 mol) of nickel acetate. 4H₂ O are suspended in 400 ml of ethylcellosolve and the suspension is warmed to 70° C. 22.93 g (0.1 mol) of the isoindolinone compound of the formula ##STR39## prepared from cyanomethylthiocarbamide and 1-imino-3-oxo-isoindoline, are then added and the mixture is heated to 110° C. It is stirred at the same temperature for 11/2 hours and then cooled to 80° C. and filtered. The material on the suction filter is washed with ethylcellosolve and ethanol and dried overnight at 80° C. in vacuo. 48.2 g (99.3% of theory) of the 1:1 nickel complex of the formula ##STR40## (only one of the possible isomeric or tautomeric forms has been considered) are obtained as a Bordeaux-red powder.

    ______________________________________                                         Microanalysis: C.sub.22 H.sub.14 N.sub.6 O.sub.2 SNi Molecular weight          485.2                                                                          ______________________________________                                         calcu-                                                                         lated*:                                                                              54.26% C 2.94% H  17.26% N                                                                               6.58% S                                                                               12.06% Ni                               found:                                                                               54.0% C  3.0% H   17.2% N 6.6% S 11.9% Ni                                      0.4                                                                            H.sub.2 O%.                                                                             (sic)                                                           ______________________________________                                          *calculated taking into account the amount of water found (0.4%)         

The above metal complex colours plastics and surface coatings in Bordeaux-red shades with excellent fastness properties.

Example 49

65 parts of stabilised polyvinyl chloride, 35 parts of dioctyl phthalate and 0.2 part of the pigment obtained according to Example 36 are stirred with one another and then worked on a twin-roll mill for 7 minutes at 140°. A red-coloured sheet with very good fastness to light and migration is obtained.

Example 50

10 g of titanium dioxide and 2 g of the pigment prepared according to Example 1 are ground with 88 g of a mixture of 26.4 g of coconut alkyd resin, 24.0 g of melamine/formaldehyde resin (50% solids content), 8.8 g of ethylene glycol monomethyl ether and 28.8 g of xylene, for 48 hours in a ball mill.

If this surface coating is sprayed onto an aluminium foil, pre-dried for 30 minutes at room temperature and then stoved for 30 minutes at 120° C., a bluish red coating is obtained, which has good colour intensity and is distinguished by a very good fastness to overcoating, light and weather.

Example 51

4 parts of the finely divided pigment according to Example 36 are stirred into 20 parts of solvent of the following composition: 50 parts of Solvesso 150 (mixture of aromatic hydrocarbons), 15 parts of butyl acetate, 5 parts of Exkin II (ketoxime-based levelling agent), 25 parts of methyl isobutyl ketone and 5 parts of silicone oil (1% in Solvesso 150).

After complete fine dispersion has been reached (in about 15-60 minutes, depending on the type of stirrer), the binders are added, i.e. 48.3 parts of Baycryl L 530 (acrylic resin) (51&(sic) in xylene/butanol 3:1) and 23.7 parts of Maprenal TTX (melamine resin) (55% in butanol).

After a short period of homogenisation, the surface coating is applied by customary methods, such as spraying and dipping or, especially for the continuous coating of metal sheets, by the "coil-coating" process, and stoved (stoving: 30 minutes, 130°). The bluish red coatings obtained are distinguished by very good levelling, high gloss and excellent fine dispersion of the pigment, and also by excellent fastness to weather.

Example 52

If the procedure described in Example 36 is repeated, except that 2.78 parts of Staybelite Resin (HERCULES) are added to the kneading mixture, a pigment containing 10% of resin is obtained, which is distinguished by being easier to incorporate and by better dispersibility. 

I claim:
 1. A 1:1 metal complex of an azine of the formula ##STR41## wherein ring A is unsubstituted or is substituted by two to four halogen atoms, by one or two alkyl of 1 to 4 carbon atoms, by one or two alkoxy of 1 to 4 carbon atoms, by phenyl, by phenoxy, by nitro, by benzoylamino or by alkanoylamino having 2 to 6 carbon atoms,R is hydrogen, alkyl of 1 to 4 carbon atoms, phenyl or naphthyl, B is phenylene, naphthylene, cyclohexenylene or a pyrazole, pyridine, pyrimidine, quinoline or coumarin radical, R₁ is OH or SH, Y is a radical of the formula ##STR42## in which Z is an O or S atom, n is the number 1 or 2 and R₂ is an alkyl, aralkyl, cycloalkyl or aryl radical or an amino group which is unsubstituted or substituted by an alkyl, cycloalkyl, aralkyl or aryl radical, and the metal is selected from the group consisting of zinc, cadmium, manganese, cobalt, iron, copper and nickel.
 2. A metal complex of the formula ##STR43## in which M is nickel or copper, R' is H or methyl, B' is a quinoline radical and Y' is a radical of the formula ##STR44## in which R₃ is an H atom, an alkyl group having 1-4 C or a radical of the formula ##STR45## in which X₁ is an H, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulfamoyl group, an alkyl, alkoxy or alkylsulfamoyl group having 1-4 C, an alkanoylamino, alkylcarbamoyl or alkoxycarbonyl group having 2-6 C, or a phenoxy, phenylcarbamoyl or phenylsulfamoyl group which is unsubstituted or substituted by chlorine or bromine atoms or methyl groups, and X₂ is an H, chlorine or bromine atom or an alkyl or alkoxy group having 1-4 C.
 3. A metal complex according to claim 1 wherein B is a quinoline radical.
 4. A metal complex of the formula ##STR46## in which M is nickel or copper, R' is H or methyl, B' is a quinoline radical, and Y' is a radical of the formula ##STR47## in which Z is an O or S atom and R₄ is an alkyl group having 1-4 C, a cyclohexyl group, a benzyl group or a group of the formula ##STR48## in which X₁ is an H, chlorine or bromine atom, a nitro, trifluoromethyl, carbamoyl or sulfamoyl group, an alkyl, alkoxy or alkylsulfamoyl group having 1-4 C, an alkanoylamino, alkylcarbamoyl or alkoxycarbonyl group having 2-6 C, or a phenoxy, phenylcarbamoyl or phenylsulfamoyl group which is unsubstituted or substituted by chlorine or bromine atoms or methyl groups, and X₂ is an H, chlorine or bromine atom or an alkyl or alkoxy group having 1-4 C.
 5. A nickel complex according to claim 2 which has the formula ##STR49## or is an isomer or tautomer thereof. 